Polymerization of epoxy compounds



re States Jersey No Drawing. Original application June 24, 1959, Ser.No. 822,413, now Patent No. 3,016,394, dated Jan. 9,

1962. Divided and this application May 20, 1960, Ser. No. 30,452

3 Claims. (Cl. 260-2) This invention relates to the preparation ofpolymers of epoxy compounds containing an oxi-rane radical in apolymerization process utilizing a novel catalyst. The catalyticmaterial more particularly is a complex resulting from the reaction of aferric halide with cyclododecatriene-l,5, 9.

It is known that ferric chloride will catalyze the polymerization ofolefin oxides. However, the reaction takes place so rapidly as to beessentially explosive and hence is practicallyy uncontrollable. Thepresent invention provides a process for effecting this type ofpolymerization reaction which permits the reaction to be conducted undercontrollable conditions.

According to the invention a catalyst is prepared by reacting eitherFeCl or FeB-r with cyclododecatriene- 1,5,9 which, for the sake ofbrevity, is hereinafter sometimes referred to as CDT. The lattercompound can be prepared in a known manner, such as by contactingbutadiene with a catalyst formed from titanium tetrachloride and diethylaluminum chloride in a hydrocarbon solvent. It has now been discoveredthat CDT will react with ferric chloride or bromide to form aniron-containing complex which will catalyze the polymerization of epoxycompound containing an oxirane radical in a controllable manner.Hydrogen halide is also formed as a product of the reaction, and it hasfurther been discovered that removal of the hydrogen halide from thecomplex greatly improves its activity as a polymerization catalyst.

The reaction product of the ferric halide with CDT is a dark solidmaterial having a composition that has not been determined withcertainty thus far. However, tests have indicated that it includes acrystalline component having the empirical formula FeX-(CDT), wherein Xrepresents chlorine or bromine, in admixture with FeX and possibly alsowith ureacted FeX At least 70% of the iron in the product appears to bein the ferrous state.

The above-described catalytic product can be prepared simply by addingCDT to anhydrous FeCl or FeBr The reaction takes place quite readily atroom temperature and is highly exothermic. An organic solvent such aschloroform, carbon tetrachloride, diethyl ether, pentane, hexane and thelike can be included in the reaction mixture if desired, although thisis not essential. After the reactants have been mixed and the exothermis complete, it is preferable to heat the mixture for a time, forexample to a temperature in the range of 60100 C. for a time of to 60minutes. Thereafter, the reaction mixture is placed under a vacuum untilall of the volatile material has been vaporized. This removes HCl formedas a result of the reaction and improves the catalytic activity of theproduct. This procedure yields a dark solid material which constitutesthe catalyst of the present invention.

The catalyst is effective for polymerizing any epoxy compound containingan oxirane radical, such as ethylene oxide, propylene oxide,chloropropylene oxide, isobutylene tent O 3,099,628 Patented July 30,1963 oxide, styrene oxide and the like. The polymerization can becarried out at temperatures in the range of 0-158 C., with the reactionrate increasing as the temperature is increased. A solvent such aspentane, hexane, isooctane, benzene, toluene, petroleum ether or diethylether can be used if desired, although the use of a solvent is notrequired. The resulting polymerization product is a mixture of amorphousand crystalline polymers which are easily separable from each other bymeans of cold acetone, the amorphous material being soluble thereinwhile the crystalline material is insoluble when the temperature of theacetone is below about 20 C. The amorphous polymer is an oily materialsuitable for use as a synthetic lubricant, and the crystalline materialcan be utilized to make molded articles, film and the like.

The following example is a specific illustration of the invention:

A catalyst is prepared by adding 15 ml. of CDT to 5.0 g. of anhydrousFeCl at room temperature in a polymerization tube. After the exothermicreaction has stopped, the mixture is heated at C. for about 30 minutes.The mixture is then placed under a vacuum until the HCl has been removedfrom it. g. of propylene oxide are added to the tube and the mixture isgently agitated 'at room temperature for 9-6 hours. At the end of thistime, 2500 ml. of acetone are added and the mixture is chilled to atemperature of about 25 C. The insoluble crystalline polymer is thenseparated from the amorphous material which remains in solution in theacetone. In this manner 40 g. of white solid polymer are obtained, andupon evaporating the acetone 36 g. of a viscous amorphous polymer areleft as residue.

This application is a division of my copending application Serial No.822,413, filed June 24, 1959, now Pratent 3,016,394.

Iclaim:

1. Method of preparing a polymer which comprises contacting an epoxycompound selected from the group consisting of ethylene oxide, propyleneoxide, chloropropylene oxide, isobutylene oxide and styrene oxide at atemperature in the range of 01'50 C. with a catalyst consistingessentially of a complex formed by reacting a ferric halide selectedfrom the group consisting of FeCl and FeBr with cyclododecatriene-1,5,9and by removing from the product HCl resulting from the reaction.

2. Method for preparing polyethers which comprises contacting an epoxycompound containing an oxirane radical and having the general formulawherein R is selected from the group consisting of alkyl, =aralkyl, andhaloalkyl radicals, at a temperature in the range of O-l50 C. with acatalyst consisting essentially of a complex [formed by reacting aferric halide selected from the group consisting of FeCl and FeBr withcyclo- -dodecatriene-1,5,9 and by removing from the product HClresulting from the reaction.

3. Method according to claim 2 wherein the ferric halide is PeClReferences Cited in the file of this patent UNITED STATES PATENTS2,811,491 Pruitt et a1. Oct. 29', 19 57

1. METHOD OF PREPARING A POLYMER WHICH COMPRISES CONTACTING AN EPOXY COMPOUND SELECTED FROM THE GROUP CONSISTING OF ETHYLENE OXIDE, PROPYLENE OXIDE, CHLOROPROPYLENE OXIDE, ISOBUTYLENE OXIDE AND STYRENE OXIDE AT A TEMPERATURE IN THE RANGE OF 0-150*C. WITH A CATALYST CONSISTING ESSENTIALLY OF A COMPLEX FORMED BY REACTING A FERRIC HALIDE SELECTED FROM THE GROUP CONSISTING OF FECL3 AND FEBR3 WITH CYCLODODECATRIENE-1,5,9 AND BY REMOVING FROM THE PRODUCT HCL RESULTING FROM THE REACTION. 